KR100747074B1 - Method for fabricating the nanorod by aao template and the nanorod using the method - Google Patents

Abstract

A method for fabricating nano rods using AAO template and the nano rod achieved by the same are provided to shorten a growth time of the nano rod by implementing DC electroplate. A seed metal(22) is deposited on a surface of an anodized portion(15) with nano-sized pores(20) in one side of AAO(Anodic Aluminum Oxide) template, and then is electroplated to form a substrate metal. The aluminum substrate is etched, except for the substrate metal and the anodized portion. A barrier layer(32) forming a lower end of the pores is removed to open the pores. The pores are immersed in an electroplating solution to fill the pores with metal. The anodized portion is etched to expose nano metals formed in pores.

Description

Method for fabricating the nanorods using anodized aluminum oxide template (AOO Ｔｅｍｐｌａｔｅ) and nanorods obtained using the same {Method for Fabricating the Nanorod by AAO Template and the Nanorod Using the Method}

       Figure 1a) to 1c) is a process flow diagram showing a step of manufacturing a nanorod using an alternating current electroplating method according to the prior art;

       Figure 2a) to 2e) shows a step of manufacturing a nanorod using a direct current electroplating method according to the prior art, a process showing the configuration of depositing a metal in AAO, then removing the AAO and electroplating Flow chart;

      3A) to 3G) illustrate stepwise a method of manufacturing a nanorod using an AAO template according to the present invention, in which a metal substrate is formed by plating a metal on AAO, followed by electroplating. A process flowchart showing a configuration to make;

       Figures 4a) to 4c) is a block diagram showing an anodized aluminum oxide (AAO Template) used in the method of manufacturing a nanorod according to the present invention,

       a) drawing cutaway section, b) drawing longitudinal section, c) drawing plan view;

       FIG. 5 is a photograph of Ni nanorods fabricated using an AO template and Ni metal according to the present invention; FIG.

       6 is a graph showing the results of detecting and analyzing the components of the Ni nanorods obtained by the present invention;

       7 is a graph showing the results of detecting and analyzing the X-ray component of the Ni nanorods obtained by the present invention.

       <Explanation of symbols for main parts of the drawings>

10 .... AAO Template

15 .... anodized part 20 .... micropores

22 .... seed metal 25 .... substrate metal

32 .... barrier layer 40 ... nanorod

100 ... Ni nanorod

200,300 .... AAO Template

205,305 .... Anodic oxidation part 210,310 ....

212,312 .... barrier layer 220,340 .... metal

330 .... seed metal

       The present invention relates to a method for manufacturing a nanorod (nanorod) and a nanorod obtained by using the same, and more particularly to uniform length and diameter by using an anodized aluminum template (AAO Template) and direct current (DC) electroplating method The present invention relates to a method for producing a nanorod having a high density and a large area with a nanorod obtained by using the method.

In the current electronic device industry, the miniaturization and high integration of devices are rapidly progressing, thereby increasing the need for nanoscale ultrafine patterns in the past micropatterns. Techniques for making such nanopatterns or nanostructures include E-Beam lithography, Scanning Tunneling Microscope (STM), and Atomic Force Microscope (AFM). Nanostructures can be fabricated.

However, it has very expensive equipment and a lot of time-consuming disadvantages, so there is a practical problem in making a large or large area of nano dots, nano wires and nano tubes (nano tube).

Therefore, as an alternative to the typical electron beam transfer industry, a large-area high-aligned nanostructure is fabricated and applied to nanometal magnetism, which is applicable not only for basic research of nanomagnetism but also for radiation action, magnetic sensing, and highly integrated magnetic circuit. For line array studies, it is important to achieve an economical, efficient and highly aligned array.

To date, the industry has demonstrated that an AAO Template, known to be physically and chemically stable, is highly capable of producing low cost, high yield, large area nanorods and nanowire arrays. Various metals, such as Ni, Fe, and Ag, have been electrodeposited through nanochannels to date by alternating current (AC) electrodeposition techniques. In addition, many electrodeposition methods using aqueous solutions lack the length uniformity of nanostructures or suffer from many disadvantages in control. In addition, AC electrodeposition technology has a disadvantage that takes a lot of time.

1 shows a related art related thereto.

This conventional technique uses an AAO template 200, which is a nano-aluminum template (AAO Template 200) is a plurality of nano-sized micropores 210 in the anodic oxidation unit 205 Are formed (see FIG. 1A).

In addition, the AAO template 200 may etch a barrier layer 212 forming a bottom of the micropores 210 formed in the anodic oxidation unit 205 to form micropores from the aluminum material. (210) Inward conductivity is secured (see FIG. 1B).

Next, alternating electroplating is performed to fill the metal 220, for example, Ni metal, in the AAO template 200 through the respective micropores 210 (see FIG. 1C). )

The AO Template 200 is then removed to obtain Ni nanorods with Ni metal 220 solidified.

However, the conventional technique as described above has a problem in that the filling property of the plating metal 220 is poor in the micropores 210 formed in the AAO template 200. That is, there are many portions in which the plating metal 220 is not filled in the micro-pores 210, which is more severe as the thickness of the template 200 becomes thicker.

In addition, since this method uses an AC electrodeposition technology, it is difficult to obtain a nanorod having a uniform length, and the end of the nanorod is not smooth. It takes a long time and is difficult to control by using an alternating current as an electrodeposition current. There is a problem.

2 illustrates a conventional method using a direct current (DC) electroplating method.

This conventional technique also uses the AO Template 300, the AO Template 300 is a plurality of nano-sized micropores 310 in the anodic oxidation unit 305 Is formed (see Fig. 2a).

In addition, the step of removing the aluminum substrate except the anodization unit 305 of the AAO template 300 by etching is performed (see FIG. 2B).

Next, the barrier layer 312 forming the bottom of the micropores 310 formed in the anodic oxidation unit 305 of the AAO template 300 is etched and removed, and the micropores 310 ) Open the bottom (see Figure 2c).

In addition, the surface of the anodization unit 305 in which the micropores 310 of the AAO template 300 are formed is deposited with a seed metal 330, for example, Ni metal. See FIG. 2D)

The process of depositing the seed metal 330 on the anodic oxidation unit 305 may use a general vacuum deposition method.

Next, the AAO Template 300 is placed in an electroplating bath (not shown), and when the DC electroplating is performed at a predetermined temperature and current density, the metal 340 is formed in the micropores 310. For example, Ni metal is filled and plated (see FIG. 2E).

In addition, in order to finally obtain a nanorod, the anodizing portion 305 is removed by etching, and a plurality of Ni nano metals 340 formed in the micropores 310 are exposed to the outside.

That is, this conventional technique opens the bottom of the micropores 310 of the AAO Template 300, deposits the metal to the extent that the micropores 310 are not blocked, and then uses DC electroplating. The rod is formed.

However, such a conventional technique also has a problem in that the filling property of the plating metal 340 is poor in the micropores 310 formed in the AAO template 300, and the thickness of the template 300 is thick. There is a problem that gets worse.

In addition, although this method uses a direct current (DC) electrodeposition technique, the current distribution formed in each of the micropores 310 formed in the AAO template 300 is uneven, so that a uniform length can be obtained. Another problem is that it is difficult to obtain nanorods.

In particular, if a defect occurs during the deposition of metal, there is a problem that causes a large number of defects in the production of nanorods during the plating operation.

In addition, such a conventional technique is applicable to thick film templates having a thickness of several tens of micrometers, and a thin film template has a problem in that its shape is difficult to maintain. Therefore, the need for a thick film template in this way also had a problem that a lot of production time is required.

The present invention is to solve the above conventional problems, the purpose is to improve the anodized aluminum oxide (AAO Template) to obtain a more large uniform nano-rod using a direct current (DC) as electrodeposition power source (AAO Template) It is an object of the present invention to provide a method for producing nanorods and nanorods obtained using the same.

In addition, the present invention provides an improved anodized aluminum template (AAO) to control the growth rate of the nanorods and to have a desired length and diameter to easily obtain a uniform array of magnetic metal nano pillars of a single domain to form an ultra high density storage medium. The purpose of the present invention is to provide a method for manufacturing a nanorod using a template and a nanorod obtained by using the same.

In order to achieve the above object, the present invention provides a method for manufacturing a nanorod (nanorod),

Depositing a surface of an anodized portion in which a plurality of nano-sized micropores are formed with a seed metal in one side of an AAO template;

Electroplating metal on the seed metal layer to form a substrate metal;

Etching removing the aluminum substrate excluding the substrate metal and the anodization portion of the AAO Template;

Removing each barrier layer forming a plurality of micropore hems formed in the anodic oxidation unit to open each micropore;

Dipping the open micropores of the anodic oxidation part in an electroplating (Watt) solution and filling the metal into the micropores by direct current (DC) electroplating; And

And removing the anodized portion by etching and exposing the plurality of nano metals formed in the micropores. .

And preferably, the anodized aluminum oxide (AAO Template) is anodized on one side of the aluminum substrate to form an anodized portion, the anodized portion is characterized in that a plurality of nano-sized micropores are formed Provided is a method for fabricating nanorods using an AAO template.

In addition, the present invention, in the nanorod (nanorod) having a large area of high alignment nanostructure,

A substrate metal obtained by electroplating a metal on a seed metal layer deposited on an AAO Template; And

Providing a nano-rod comprising a; a plurality of nano-metals which are integrally protruded by direct current electroplating on the substrate metal, and are exposed to the outside by removing the aluminum oxide template (AAO Template).

And the present invention preferably provides a nano-rod, characterized in that the plurality of nano-metals having a uniform diameter and length.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.

As shown in FIG. 3, the present invention utilizes an anodized aluminum template (AAO Template) 10 and uses a direct current (DC) electroplating method to fabricate nanorods of uniform length and high density. 100).

To this end, the present invention prepares the anodized aluminum template 10, which is anodized on one side of the aluminum substrate to form an anodized portion 15, as shown in Figs. 4a), 4b) and 4c). As described above, a plurality of nano-sized micropores 20 are formed in the anodic oxidation unit 15 (see FIG. 3A).

The anodized aluminum template 10 is an electropolishing of the anodizing unit 15 to remove surface foreign matters prior to anodizing an aluminum substrate, and 0.3 mol% oxalic acid solution containing oxalic acid in ion-exchanged water as an electrolyte. Anodized using

Then, by using the anodized aluminum template 10 as described above, the present invention deposits the surface of the anodic oxidation part 15 in which a plurality of nano-sized micropores 20 are formed as a seed metal 22. Go through the steps (see Figure 3b).

A process of depositing such a seed metal 22 on the anodization part 15 of the anodized aluminum template 10 is common, and heats the anodized aluminum template 10 to a predetermined temperature and is heated. A general vacuum deposition method for depositing a metal evaporation material on the surface of the anodic oxidation unit 15 may be used.

In this case, the metals to which the present invention is applied may be, for example, Ni, Cu, Cr, Sn, Cd, Pb, Ag, Au, Rd, Pt, Pd, In, Ru, and various alloys thereof.

In addition, the present invention includes the step of forming a substrate metal 25 by electroplating the same metal as the seed metal on the seed metal layer 22 (see FIG. 3C).

In this process, electroplating is used, Ni is used as a seed metal, and Ni is electroplated using a solution containing nickel sulfate, ammonium chloride, boric acid solution, or nickel chloride in ion-exchanged water. Ni is electroplated on the seed metal 22 layer by flowing an electric current by using the anode as the anode and the anodized aluminum template 10 as the cathode.

Since the electroplating method may use a method commonly used in the art, a detailed description thereof will be omitted.

If the seed metal is other than Ni, the metal to be electroplated is the same as the seed metal, for example, Cu, Cr, Sn, Cd, Pb, Ag, Au, Rd, Pt, Pd, In, Ru And any of these various alloys.

When the substrate metal 25 is thickly deposited on the anodized aluminum template 10 as described above, an aluminum substrate except for the substrate metal 25 and the anodized portion 15 of the anodized aluminum template 10 is next formed. Removal is by etching.

Thus, in order to remove the metal aluminum constituting the aluminum substrate by etching, CuCl ₂ in ion-exchanged water And 0.1 mol% CuCl ₂ with HCl With 20 wt% HCl solution (see FIG. 3D).

Next, a step of opening the respective micropores 20 by removing the barrier layer 32 forming the bottoms of the plurality of micropores 20 formed in the anodic oxidation unit 15 is performed.

In the anodized aluminum oxide template 10 in which the metal aluminum constituting the aluminum substrate is removed, a barrier layer 32 is formed at the bottom of the plurality of micropores 20, and the barrier layer 32 is an ion. H ₃ PO ₄ in Attendant This is removed using the contained 6 wt% H ₃ PO ₄ solution. As such, when the barrier layer 32 is removed from each of the micropores 20, each of the micropores 20 is open at a lower end thereof so that the inside and the outside of the micropores 20 communicate with each other. The metal 40 may be filled in the anodized aluminum template 10 through (see FIG. 3E).

Then, the present invention is to dip the open micropores 20 of the anodic oxidation unit 15 in the electroplating (Watt) solution, DC electroplating to fill the metal 40 in each micropores 20 Is done.

That is, when the anodized aluminum oxide template 10 is placed in an electroplating bath and plated at a predetermined temperature and current density, the metals 40 are filled in the micropores 20 and plated. See 3f)

In this case the metal to be electroplated is the same metal as the seed metal and the substrate metals.

And the present invention is to remove the anodic oxidation portion 15 by etching to obtain the final nanorod 100, and to expose a plurality of metals 40 formed in the micro-pores 20 to the outside Include.

In this step, anodized aluminum template in 6wt% H ₃ PO ₄ + 1.8wt% CrO ₃ solution containing H ₃ PO ₄ and CrO ₃ in ion-exchanged water in order to etch the anodized portion 15. The anodic oxidation portion 15 except for the substrate metal 25 and the nano metals may be removed by dipping the 10.

By removing the anodic oxidation portion 15 as described above, a desired nanorod 100 can be obtained, which is composed of a substrate metal 25 and a plurality of nano metals 40 protruding from the substrate metal 25. (See Fig. 3g).

In this structure, the anodized aluminum template 10 is removed, and a plurality of nano metals 40 protrude from the substrate metal 25 in a predetermined length to form the nano rod 100.

5 shows a photograph of the Ni nanorods 100 obtained by using the present invention. In the Ni nano rod 100 as described above, it can be seen that each of the Ni nano metals 40 has a length of 500 nm and is uniformly grown from the Ni substrate metal 25.

In the above, Ni nanorods 40 were obtained using Ni. However, if a metal other than Ni is used, for example, Cu, Cr, Sn, Cd, Pb, Ag, Au, Rd, Pt, Pd, In, Nano metal can be obtained using any one of Ru and these various alloys.

Hereinafter, a series of experiments were conducted to demonstrate the effect of the present invention.

The present invention used a metal aluminum (Al 1080) 0.5t plate (Plate) as a material for the fabrication of the anodized aluminum (AAO) template 10 and the size of the specimen was cut to 60mm length 60mm. And Ni was used to obtain Ni nanorods.

First, the aluminum aluminum plate was anodized to prepare an anodized aluminum (AAO) template 10 having an anodization unit 15 in which a plurality of micropores 20 each having a diameter of 80 to 100 nm was formed.

Next, a Ni seed metal 22 is deposited on the anodized aluminum (AAO) template 10 for electroplating the Ni metal to be a substrate, and then the Ni substrate metal 25 is electroplated thereon. It was deposited thick.

A barrier layer is then removed from the aluminum material portion of the anodized aluminum oxide (AAO) template 10 with 0.1 mol% CuCl ₂ + 20 wt% HCl solution followed by a 6 wt% H ₃ PO ₄ solution to form the lower end of the micropores 20. (32) was removed.

In addition, the anodized aluminum oxide (AAO) template 10 having the barrier layer 32 removed as above was immersed in a Ni electroplating (Watt) solution, and maintained at a current density of 5 (A / m ² ) at 20 ° C. for 5 minutes. Plated.

The anodized aluminum oxide (AAO) template 10 was then removed, followed by 6 wt% H to observe the Ni nanorods 100.₃PO₄ + 1.8 wt% CrO₃  After etching at 30 ° C. for 3 hours, the Ni nanorods 100 could be observed using a scanning electron microscope (FESEM).

Ni nano rod 100 manufactured as described above was a state in which a plurality of Ni nano metals 40 are uniformly grown to a length of 500nm on the Ni substrate metal 25, it was observed as shown in FIG. The composition and structure of the grown Ni nanorods 100 were analyzed and observed using XRD equipment and FE-SEM (JEOL 7000F).

Figure 6 measured the components of the Ni nanorods 100 obtained in the present invention using the Oxford EDS equipment. As a result of the measurement, only 100% Ni peak was observed in the Ni nanorod 100 of the present invention, which indicates that the high purity Ni nanorod 100 was obtained.

7 shows the X-ray pattern of the Ni nanorods 100, which also shows that only Ni peaks are measured, and that the Ni nanorods 100 of high purity are obtained.

Although the present invention has been described in detail with reference to the drawings with reference to specific embodiments, the present invention is not limited to any such specific metal. Those skilled in the art may variously modify or change the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. In particular, although a series of experiments were performed using the Ni metal, the present invention is not limited thereto, and a metal capable of electroplating other than Ni, for example, Cu, Cr, Sn, Cd, Pb, Ag, Au, Rd , Pt, Pd, In, Ru, and various alloys thereof, it can be seen that it can be easily applied to the process of manufacturing nanorods. Therefore, it is intended that such modifications or modified metals are all clearly within the scope of the present invention.

       As described above, according to the present invention, a large-area uniform nanorod can be obtained using direct current (DC) as the electrodeposition power source.

In addition, the present invention can shorten the growth time of the nanorods by performing direct current (DC) electroplating, rather than alternating current (AC) electroplating.

In addition, the present invention can control the growth rate of the nanorods, and by controlling to have the desired length and diameter can easily obtain a uniform magnetic metal nano-pillar array of a single domain, thereby easily obtaining an ultra-high density storage medium will be.

In addition, since the present invention can manufacture a nanorod using an anodized aluminum template made of a commercially available aluminum sheet material, it is economically possible to manufacture a large-area high-density nanorod.

Claims (10)

In the method for producing a nanorod (nanorod), Depositing a surface of an anodized portion in which a plurality of nano-sized micropores are formed with a seed metal in one side of an AAO template; Electroplating metal on the seed metal layer to form a substrate metal; Etching removing the aluminum substrate excluding the substrate metal and the anodization portion of the AAO Template; Removing each barrier layer forming a plurality of micropore hems formed in the anodic oxidation unit to open each micropore; Dipping the open micropores of the anodic oxidation portion in a watt solution and filling the metal in the micropores by direct current (DC) electroplating; And Etching to remove the anodized portion and exposing a plurality of nano metals formed in the micropores. 10.        The method of claim 1, wherein the anodized aluminum template (AAO Template) to anodize one side of the aluminum substrate to form an anodized portion, characterized in that a plurality of nano-sized micropores are formed in the anodized portion Method of manufacturing nanorods using AAO Template.        The method of claim 1, wherein the seed metal, the substrate metal, and the nano metals are the same metal.        4. The method of claim 3, wherein the seed metal, the substrate metal, and the nano metals are any one of a metal capable of electroplating. 5.        The method of claim 4, wherein the seed metal, the substrate metal, and the nano metals are any one of Ni, Cu, Cr, Sn, Cd, Pb, Ag, Au, Rd, Pt, Pd, In, Ru, and various alloys thereof. Method for producing a nanorod using anodized aluminum oxide (AAO Template), characterized in that. In a nanorod having a large area of high alignment nanostructure, A substrate metal obtained by electroplating a metal on a seed metal layer deposited on an AAO Template; And And a plurality of nano metals protruded integrally by DC electroplating on the substrate metal and exposed to the outside by removing the aluminum oxide template (AAO Template).       The nanorod of claim 6, wherein the plurality of nanometals have a uniform diameter and length.        The nanorod of claim 6, wherein the seed metal, the substrate metal, and the nano metals are the same metals.        The nanorod of claim 8, wherein the seed metal, the substrate metal, and the nano metals are any one of metals capable of electroplating.        The method of claim 9, wherein the seed metal, the substrate metal, and the nano metals are any one of Ni, Cu, Cr, Sn, Cd, Pb, Ag, Au, Rd, Pt, Pd, In, Ru, and various alloys thereof. Nanorod, characterized in that.

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